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Triphenylphosphine → (3aR,4R,5R,6R,7aS)-4,5-Bis(benzyloxy)-6-((benzyloxy)methyl)-2-(pyrrolidin-1-yl)-3a,4,5,6,7,7a-hexahydrobenzo[d]thiazole

HRID 2274310
Notes
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Reaction equation

HRID 2274310 reaction equation
[CH2:1]([O:8][C@H:9]1[C@H:14]([O:15][CH2:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[C@@H:13]([CH2:23][O:24][CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[CH2:12][C@@H:11](O)[C@@H:10]1[NH:33][C:34]([N:36]1[CH2:40][CH2:39][CH2:38][CH2:37]1)=[S:35])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C>C1COCC1>[CH2:1]([O:8][C@@H:9]1[C@H:10]2[N:33]=[C:34]([N:36]3[CH2:40][CH2:39][CH2:38][CH2:37]3)[S:35][C@H:11]2[CH2:12][C@H:13]([CH2:23][O:24][CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[C@H:14]1[O:15][CH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

5

Reactant 3

HCID 11776TriphenylphosphineHCID 5363146Diisopropyl azodicarboxylateHCID 86727204N-((1S,2R,3R,4R,6R)-2,3-bis(benzyloxy)-4-((benzyloxy)methyl)-6-hydroxycyclohexyl)pyrrolidine-1-carbothioamide

Product 1

HCID 67480335(3aR,4R,5R,6R,7aS)-4,5-Bis(benzyloxy)-6-((benzyloxy)methyl)-2-(pyrrolidin-1-yl)-3a,4,5,6,7,7a-hexahydrobenzo[d]thiazoleYield 84%

Reagents, catalysts & solvents

1
HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of N-((1S,2R,3R,4R,6R)-2,3-bis(benzyloxy)-4-((benzyloxy)methyl)-6-hydroxycyclohexyl)pyrrolidine-1-carbothioamide (0.260 g, 0.464 mmol) and triphenylphosphine (0.183 g, 0.700 mmol) in anhydrous THF (6.0 mL) was added DIAD (0.131 g, 0.650 mmol). After addition the mixture was stirred at room temperature for 60 h. The solvent was evaporated under reduced pressure, and the residue was purified on silica gel by automatic flash column chromatography (EtOAc/hexanes, 1:10 to 1:4), affording as a colorless oil (0.21 g, 84%). 1H NMR (400 MHz, CDCl3) δ 7.43-7.42 (m, 2H), 7.34-7.23 (m, 13H), 4.95 (d, J=11.6 Hz, 1H), 4.86 (d, J=11.0 Hz, 1H), 4.76 (d, J=11.6 Hz, 1H), 4.56 (d, J=11.0 Hz, 1H), 4.50-4.43 (m, 2H), 3.80 (d, J=7.6 Hz, 1H), 3.78-3.76 (m, 2H), 3.68 (dd, J=4.0, 9.0 Hz, 1H), 3.57-3.43 (m, 4H), 3.13 (d, J=6.2 Hz, 1H), 2.89-2.88 (m, 1H), 2.28-2.23 (m, 1H), 2.05-2.02 (m, 1H), 2.00-1.90 (m, 4H), 1.87-1.82 (m, 1H).

Workup

  1. additionAfter addition the mixture
  2. customThe solvent was evaporated under reduced pressure
  3. customthe residue was purified on silica gel by automatic flash column chromatography (EtOAc/hexanes, 1:10 to 1:4)

Sources & evidence

ORD record
ord-3fd5a4b4f3cf4287b813904f385384d0
Source dataset
uspto-grants-2015_09
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US09126957B2

Reaction notes

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On this pageParticipantsProcedureWorkupSources & evidenceReaction notes